Controlling the Interactions between Soft Colloids via Surface Adsorption

By employing monomer-resolved computer simulations and analytical considerations based on polymer scaling theory, we analyze the conformations and interactions of multiarm star polymers strongly adsorbed on a smooth, two-dimensional plane. We find a stronger stretching of the arms as well as a stronger repulsive, effective interaction than in the three dimensional case. In particular, the star size scales with the number of arms $f$ as $\sim f^{1/4}$ and the effective interaction as $\sim f^{2}$, as opposed to $\sim f^{1/5}$ and $\sim f^{3/2}$, respectively, in three dimensions. Our results demonstrate the dramatic effect that geometric confinement can have on the effective interactions and the subsequent correlations of soft colloids in general, for which the conformation can be altered as a result of geometrical constraints imposed on them.Comment: 17 pages, LaTeX, 5 figures, to appear in Macromolecule

Effect of bending rigidity on the knotting of a polymer under tension

A coarse-grained computational model is used to investigate how the bending rigidity of a polymer under tension affects the formation of a trefoil knot. Thermodynamic integration techniques are applied to demonstrate that the free-energy cost of forming a knot has a minimum at non-zero bending rigidity. The position of the minimum exhibits a power-law dependence on the applied tension. For knotted polymers with non-uniform bending rigidity, the knots preferentially localize in the region with a bending rigidity that minimizes the free-energy.Comment: 15 pages, 6 figures. Corrected problem with references to equation

Phase separation of a multiple occupancy lattice gas

A binary lattice gas model that allows for multiple occupancy of lattice sites, inspired by recent coarse-grained descriptions of solutions of interacting polymers, is investigated by combining the steepest descent approximation with an exploration of the multidimensional energy landscape, and by Gibbs ensemble Monte Carlo simulations. The one-component version of the model, involving on site and nearest neighbour interactions, is shown to exhibit microphase separation into two sub-lattices with different mean occupation numbers. The symmetric two-component version of the multiple occupancy lattice gas is shown to exhibit a demixing transition into two phases above a critical mean occupation number.Comment: submitted to Journal of Physics

Fluid-fluid demixing transitions in colloid--polyelectrolyte star mixtures

We derive effective interaction potentials between hard, spherical colloidal particles and star-branched polyelectrolytes of various functionalities and smaller size than the colloids. The effective interactions are based on a Derjaguin-like approximation, which is based on previously derived potentials acting between polyelectrolyte stars and planar walls. On the basis of these interactions we subsequently calculate the demixing binodals of the binary colloid--polyelectrolyte star mixture, employing standard tools from liquid-state theory. We find that the mixture is indeed unstable at moderately high overall concentrations. The system becomes more unstable with respect to demixing as the star functionality and the size ratio grow.Comment: 24 pages, 9 figures, submitted to Journal of Physics: Condensed Matte

Structure, phase behavior and inhomogeneous fluid properties of binary dendrimer mixtures

The effective pair potentials between different kinds of dendrimers in solution can be well approximated by appropriate Gaussian functions. We find that in binary dendrimer mixtures the range and strength of the effective interactions depend strongly upon the specific dendrimer architecture. We consider two different types of dendrimer mixtures, employing the Gaussian effective pair potentials, to determine the bulk fluid structure and phase behavior. Using a simple mean field density functional theory (DFT) we find good agreement between theory and simulation results for the bulk fluid structure. Depending on the mixture, we find bulk fluid-fluid phase separation (macro-phase separation) or micro-phase separation, i.e., a transition to a state characterized by undamped periodic concentration fluctuations. We also determine the inhomogeneous fluid structure for confinement in spherical cavities. Again, we find good agreement between the DFT and simulation results. For the dendrimer mixture exhibiting micro-phase separation, we observe rather striking pattern formation under confinement.Comment: 8 pages, 10 figure

Studying synthesis confinement effects on the internal structure of nanogels in computer simulations

We study the effects of droplet finite size on the structure of nanogel particles synthesized by random crosslinking of molecular polymers diluted in nanoemulsions. For this, we use a bead-spring computer model of polymer-like structures that mimics the confined random crosslinking process corresponding to irradiation- or electrochemically-induced crosslinking methods. Our results indicate that random crosslinking under strong confinement can lead to unusual nanogel internal structures, with a central region less dense than the external one, whereas under moderate confinement the resulting structure has a denser central region. We analyze the topology of the polymer networks forming nanogel particles with both types of architectures, their overall structural parameters, their response to the quality of the solvent and compare the cases of non-ionic and ionic systems

Dynamics in binary cluster crystals

As a result of the application of coarse-graining procedures to describe complex fluids, the study of systems consisting of particles interacting through bounded, repulsive pair potentials has become of increasing interest in the last years. A well known example is the so-called Generalized Exponential Model (GEM-$m$), for which the interaction between particles is described by the potential $v(r)=\epsilon\exp[-(r/\sigma)^m]$. Interactions with $m > 2$ lead to the formation of a novel phase of soft matter consisting of cluster crystals. Recent studies on the phase behavior of binary mixtures of GEM-$m$ particles have provided evidence for the formation of novel kinds of alloys, depending on the cross interactions between the two species. This work aims to study the dynamic behavior of such binary mixtures by means of extensive molecular dynamics simulations, and in particular to investigate the effect of the addition of non-clustering particles on the dynamic scenario of one-component cluster crystals. Analogies and differences with the one-component case are revealed and discussed by analyzing self- and collective dynamic correlators.Comment: 17 pages, 8 figures, submitted to JSTA

Density functional theory for the freezing of soft-core fluids

We present a simple density functional theory for the solid phases of systems of particles interacting via soft-core potentials. In particular, we apply the theory to particles interacting via repulsive point Yukawa and Gaussian pair potentials. We find qualitative agreement with the established phase diagrams for these systems. The theory is able to account for the bcc-fcc solid transitions of both systems and the re-entrant melting that the Gaussian system exhibits.Comment: 7 pages, 4 figure

Generation of defects and disorder from deeply quenching a liquid to form a solid

We show how deeply quenching a liquid to temperatures where it is linearly unstable and the crystal is the equilibrium phase often produces crystalline structures with defects and disorder. As the solid phase advances into the liquid phase, the modulations in the density distribution created behind the advancing solidification front do not necessarily have a wavelength that is the same as the equilibrium crystal lattice spacing. This is because in a deep enough quench the front propagation is governed by linear processes, but the crystal lattice spacing is determined by nonlinear terms. The wavelength mismatch can result in significant disorder behind the front that may or may not persist in the latter stage dynamics. We support these observations by presenting results from dynamical density functional theory calculations for simple one- and two-component two-dimensional systems of soft core particles.Comment: 25 pages, 11 figure